• Bulletin of the Korean Chemical Society
• /
• v.24 no.2
• /
• pp.205-208
• /
• 2003

Laser-induced Raman spectroscopy has been utilized to demonstrate its feasibility for studying the kinetics of imine formation in chloroform solvent. The imine formation, by the nucleophilic addition of primary amine to the carbonyl group of ketone, has been monitored at ten minute intervals for eight hours. The intensity of the C=O stretching mode at 1684 $cm^{-1}$ was measured to determine the rate constant of the reaction. In order to correct the sample-to-sample fluctuations in Raman peak area, this peak was normalized to the C-Cl bending peak at 666 $cm^{-1}$. By the peak area change during the course of reaction, the second order rates at three different temperatures have been determined. The substituent effects on the π conjugations of imine product have also been investigated. On the basis of Raman frequency shifts, the delocalization properties of the aromatic system modified by substitution of a hydrogen atom with -Cl and $-CH_3O$ groups could be clearly understood.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.11
• /
• pp.3279-3282
• /
• 2010

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2$, CN, $CF_3$) with Y-substituted benzylamines (Y = p-$OCH_3$, p-$CH_3$, H, p-Cl) in MeOH-MeCN mixtures were measured by conductometry at $25^{\circ}C$. It was observed that the rate constant increased in the order of X = $NO_2$ > CN > $CF_3$ and in the order of Y = p-$OCH_3$ > p-$CH_3$ > H > p-Cl. When the solvent composition was varied, the rate constant increased in the order of 100% MeOH < 50% (v/v) MeOH-MeCN < 100% MeCN. These results may be ascribed to the formation of hydrogen bonds between the alcoholic hydrogen and nitrogen of benzylamines in groud state (GS). We conclude that the reaction takes place via $S_NAr$ base on the transition state parameters ${\rho}x$, ${\rho}Y$, $\beta_{nuc}$, and solvent effects.

• Journal of the Korean Applied Science and Technology
• /
• v.10 no.1
• /
• pp.67-74
• /
• 1993

1, 2-Isopropylidene glycerol produced by ketalyzation of glycerol with aceton was esterified with long chain fatty acids in the presence of a Mucor miehei lipase to obtain 1, 2-isopropylidene 3-long chain acyl glycerol. To determine optimal conditions for the esterification reaction, esterification was proceeded as a reversible second-order reaction in various parameters that are enzyme/substrate ratio 0.096g/g at reaction temperatures ranged from $25^{\circ}C$ to $70^{\circ}C$. The order of reaction rate of fatty acids were lauric acid, myristic acid, oleic acid, and stearic acid. The range of their activation energies were from 7.8 to 11.4 (kcal/mol) and that of entropies of activation which have negative values were from 42.8 to 52.5(e.u.).

• Bulletin of the Korean Chemical Society
• /
• v.13 no.5
• /
• pp.511-516
• /
• 1992

The catalytic oxidation of CO on perovskite $Eu_{1-x}Sr_xCoO_{3-y}$, has been investigated at reaction temperatures from 100 to $250^{\circ}C$ under stoichiometric CO and $O_2$ partial pressures. The microstructure and Sr-substitution site of the catalyst were studied by means of infrared spectroscopy. The reaction rates were found to be correlated with 1.5-and 1.0-order kinetics with and without a $CO_2$ trap, respectively; first-and 0.5-order with respect to CO and 0.5-order to $O_2$ with the activation energy of 0.37 eV $mol^{-1}$. It was found from IR, ${\sigma}$ and kinetic data that $O_2$ adsorbs as an ionic species on the oxygen vacancies, while CO adsorbs on the lattice oxygens. The oxidation reaction mechanism is suggested from the agreement between IR, ${\sigma}$ and kinetic data.

• Bulletin of the Korean Chemical Society
• /
• v.22 no.7
• /
• pp.669-672
• /
• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• Journal of applied mathematics & informatics
• /
• v.35 no.3_4
• /
• pp.277-302
• /
• 2017

In this paper, we have proposed a numerical method for Singularly Perturbed Boundary Value Problems (SPBVPs) of reaction-diffusion type of third order Ordinary Differential Equations (ODEs). The SPBVP is reduced into a weakly coupled system of one first order and one second order ODEs, one without the parameter and the other with the parameter ${\varepsilon}$ multiplying the highest derivative subject to suitable initial and boundary conditions, respectively. The numerical method combines boundary value technique, asymptotic expansion approximation, shooting method and finite difference scheme. The weakly coupled system is decoupled by replacing one of the unknowns by its zero-order asymptotic expansion. Finally the present numerical method is applied to the decoupled system. In order to get a numerical solution for the derivative of the solution, the domain is divided into three regions namely two inner regions and one outer region. The Shooting method is applied to two inner regions whereas for the outer region, standard finite difference (FD) scheme is applied. Necessary error estimates are derived for the method. Computational efficiency and accuracy are verified through numerical examples. The method is easy to implement and suitable for parallel computing. The main advantage of this method is that due to decoupling the system, the computation time is very much reduced.

• Applied Chemistry for Engineering
• /
• v.26 no.3
• /
• pp.347-350
• /
• 2015

In this study, ionic liquids have been employed as a green catalyst in the alkylation of isobutane with 2-butene. One of acid ionic liquids, 1-octyl-3-methylimidazolium-bromide-aluminum chloride, was used in the reaction. Effects of the liquid hourly space velocity (LHSV), reaction temperature and composition of ionic liquids on the reaction performance were investigated in order to optimize reaction conditions. Under identical reaction conditions, the optimum reaction temperature was $80^{\circ}C$ and the ionic liquid with the anion composition of 0.56 showed an excellent reaction activity. Moreover, a correlation model was developed with a statistical approach to predict the product yields.

• Journal of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.19-28
• /
• 1990

The rate of chlorine-exchange reaction of antimony trichloride with benzyl, $\alpha$-phenyl ethyl and diphenyl methyl chlorides in nitrobenzene have been determined. The results indicate that the chlorine-exchange reaction follows second-order kinetics with respect to antimony trichloride and first-order kinetics with respect to organic chlorides. Rate = $k_3[SbCl_3]^2$ [Org-Cl] The rate constants of chlorine-exchange of antimony trichloride with organic chloride increase in the following order of the organic chlorides. Benzyl chloride < $\alpha$-phenyl ethyl chloride < diphenyl methyl chloride The mechanism of the chlorine-exchange reactions has been proposed.

• Analytical Science and Technology
• /
• v.30 no.2
• /
• pp.89-95
• /
• 2017

The thermodynamic functions for the binding of the peptide Substance P (SP) on the surface of lipid vesicles made of various types of lipids were obtained by using isothermal titration calorimetry. The reaction enthalpies measured from the experiments were -0.11 to $-4.5kcal\;mol^{-1}$. The sizes of the lipid vesicles were measured with dynamic light scattering instrument in order to get the correlation between the reaction enthalpies and the vesicle sizes. The bindings of SP on the lipid vesicles with diameter of 37 to 108 nm were classified into the enthalpy-driven reaction or the entropy-driven reaction according to the size of the lipid vesicles. For the enthalpy-driven binding reaction, the significance of the electrostatic interactions between SP and lipid molecules was affirmed from the experimental results of the DMPC/DMPG/DMPH and DMPC/DMPS/DMPH vesicles as well as the importance of the hydrophobic interactions between hydrophobic groups of SP and lipid molecules.

• Journal of Ginseng Research
• /
• v.14 no.2
• /
• pp.117-121
• /
• 1990

Browning intensity is a major factor to estimate the quality of red ginseng or red ginseng products. The Maillard type of browning reaction proceeds nonenzymatically during extraction and concentration of red ginseng. The present studies were carried out to investigate the effects of amino acids and sugars on the browning reaction during extraction and concentration of red ginseng. Red ginseng was pulverized to 115 mesh and then tenfold (v/w) of water was added to the powder to make the substrate of red ginseng. Solution (0.1 M) of fourteen amino acids and of folly silgars were added to the substrates of red ginseng powder and these were then extracted and concentrated to examine their browning intensities. Amino acids were more effective than sligars in acrelerating the browning reaction. Acceleration of the browning reaction in the concentrate was in the order of arginine> histidine>glycine>alanine>lysine phenyl alanine>aspartic acid>lelicine>threonine>gllitamic acid>tyrosine>valine>istleucine>methionine for amino acids, and was glucose>frlictose >silcrose, maltose for sugars.